Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
  • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
  • C07C5/05—Partial hydrogenation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • C07C2531/24—Phosphines

Definitions

• the present invention relates to a method for the partial hydrogenation of conjugated dienes to produce olefin compounds, which are useful as starting materials for useful polymers and also as starting materials for various organic fine derivatives.
• the present inventors have conducted extensive researches to find a catalyst system and reaction conditions suitable for the selective partial hydrogenation of chain conjugated dienes with conjugated two double bonds having different numbers of substituents, whereby as between the conjugated two double bonds, the one having a greater number of substituments is selectively hydrogenated.
• the present invention provides a method for the partial hydrogenation of conjugated dienes, characterized in that a chain conjugated diene in which the conjugated two double bonds have different numbers of substituents, is hydrogenated at a temperature of not higher than 50°C in the presence of a catalyst composed essentially of (1) a cobalt compound, (2) an organophosphine compound and (3) an aluminum compound, to obtain a partially hydrogenated product wherein as between said conjugated two double bonds, the one having a greater number of substituents is selectively hydrogenated.
• a catalyst system which is composed essentially of a cobalt compound, an organophosphine compound and an aluminum compound.
• cobalt compound there may be mentioned a salt such as cobalt chloride, cobalt sulfate, cobalt nitrata, cobalt carbonate, cobalt acetate, cobalt formate, cobalt naphthenate, cobalt oleate, cobalt octanoate, cobalt cyanide, cobalt fluoride, cobalt bromide or cobalt iodide; a chelate compound such as bis(acetylacetonato)-cobalt cr tris(acetylacetonato)cobalt; or an organo- phosphorus complex compound such as chlorotris(triphenylphosphine)cobalt, bromotris(tripnenylphosphine)cobalt, dichlorobis(triphenylphosphine)cobalt or dibromobis(triphenylphosphine)cobalt.
• a salt such as cobalt chloride, cobal
• a triarylphosphine such as triphenylphosphine, tris(p-methoxyphenyl)phosphine, tris(o-methoxyphenyl)phosphine, tris(p-trimethylsilyl- phenyl)phosphine, tri-p-tolylphosphine or tri-o-tolylphosphine; a trialkylphosphine such as tri-n-butylphosphine, tri-n-propylphosphine or tri-iso-propylphosphine; a triaralkylphosphine such as tribenzylphosphine; a mixed alkylarylphosphine such as diphenyl-n-propylphosphine, diphenyl-iso-propylphosphine, l-diphenylphosphino-2-trimethylsilylethane or 1,
• an organoaluminum compound such as trimethyalalminum, triethylaluminum, tri-iso-butylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, tri-n-hexylaluminum, diethylaluminumhydride, di-iso-butylaluminum hydride, diethylaluminum chloride, di-iso-butylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, iso-butylaluminum dichloride, ethylaluminum dibromide, ethylaluminum sesquichloride, iso-butylaluminum sesquichloride or ethylaluminum sesquibromide; or an inorganic aluminum compound such as aluminum chloride or aluminum bromide.
• an organoaluminum compound such as trimethyalalminum,
• the aluminum compound it is preferred to employ a combination of the above-mentioned organic aluminum compound and the inorganic aluminum compound, or a combination of a plurality of organic aluminum compounds. It is further preferred to employ a combination of an aluminum compound containing a halogen atom, i.e. an organic or inorganic aluminum compound containing a halogen atom, and an organic aluminum compound containing no halogen atom.
• a boron halide compound and/or a proton acid having a pKa of at most 1 is effective to use as an additional catalyst component.
• boron halide compound there may be mentioned boron trifluoride, boron trichloride, boron tribromide, boron trifluoride etherate (BF 3 .OEt 2 ) or a boron triflucride-dimethanol compound (BF 3 .2CH 3 OH).
• an inorganic proton acid such as sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, perchloric acid, tetrafluoroboric acid or thiocyanic acid
• an organic proton acid such as trifluoroacetic acid, trichloroacetic acid, trichloromethane sulfonic acid, trifluoromethane sulfonic acid or p-toluene sulfonic acid.
• an organic proton acid is preferably used.
• the above-mentioned cobalt compound is added usually in an amount of from 1 to 0.000001 mol, preferably from 0.1 to 0.00001 mol, as cobalt atoms, per mol of the starting material conjugated diene.
• the above-mentioned organophosphine compound is added usually in an amount of at least 0.1 mol, preferably from 1 to 1000 mol, more preferably from 1 to 100 mol, especially from 1 to 20 mol, as phosphorus atoms, per mol of the cobalt atoms in the above cobalt compound, whereby it is possible to obtain a partially hydrogenated product wherein among the conjugated double bonds, the one having a greater number of substituents is selectively hydrogenated, in high selectivity, while maintaining a high conversion of the conjugated diene.
• organophosphine compound when added in an amount of more than 20 mcl, preferably mere than 20 mol and not more than 1000 mcl, more preferably more than 20 mol and not more than 500 mol, it is pcssible to obtain a partially hydrogenated produce in which among the conjugated double bonds, the one having a greater number of substituents is selectively hydrogenated, in high selectivity even if the conversion of the conjugated diene is increased to an extremely high level.
• the above-mentioned aluminum compound is added usually in an amount of from 1 to 100 mol, preferably from 2 to 20 mol, as aluminum atoms, per mol of cobalt atoms in the above cobalt compound.
• boron halide compound in the case where a boron halide compound is used, it is added usually in an amount of from 1 to 100 mol, preferably from 1 to 10 mol, per mol of cobalt atoms in the cobalt compound.
• a proton acid having a pKa of at most 1 such a proton acid is added usually in an amount of from 1 to 100 mol, preferably from 1 to 10 mol, per mol of cobalt atoms in the cobalt compound.
• the present invention is directed to hydrogenation wherein a chain conjugated diene in which the conjugated two double bonds have different numbers of substituents, is used, and among the conjugated two double bonds, the one having a greater number of substituents is selectively hydrogenated.
• the "chain” conjugated diene means a conjugated diene in which at least cne of the conjugated two double bonds is in a chain portion.
• it includes a conjugated diene in which one of the double bonds is located in a cyclic portion and the other is located on a chain portion.
• the double bond at the specific position as shown in Table A i.e. the double bond having a greater number of substituents as between the conjugated two double bonds is selectively hydrogenated to give partially hydrogenated products.
• Such an a-olefin compound is represented by the formula : where R 1 is an aryl group, a tertiary alkyl group or a tertiary silyl group, and R 2 is a hydrogen atom, an alkyl group, a tertiary silyl group or an aryl group.
• R 1 is an aryl group, a tertiary alkyl group or a tertiary silyl group
• R 2 is a hydrogen atom, an alkyl group, a tertiary silyl group or an aryl group.
• styrene ⁇ -methylstyrene, vinylnaphthalene, 1,1-diphenylethylene, 3,3-dimethylbutene-1, adamantylethylene, vinyltrimethylsilane or l,l-bis(trimethylsilyl)ethylene.
• each of R 1 and R 2 is an alkyl group, a silyl group or an aryl group, or R 1 and R 2 may together form a ring.
• Particularly preferred among them are cis-olefins wherein R 1 and R 2 are linked to form a bridged olefin compound and the carbon atoms adjacent to the olefin portion are bridge head carbon atoms, and cis-olefins wherein each of R 1 and R 2 is a tertiary alkyl group, a tertiary silyl group or an aryl group.
• a bridged olefin such as 2-norbornene, 2,5-norbornadiene, dicyclopentadiene, bicyclo[2,2,2]octa-2-ene, bicyclo[2,2,2]octa-2,5,7-triene, bicylo[2,1,1]hexa-2-ene or bicyclo[2,2,0]hexa-2,5-diene; a cis-tertiary alkyl substituted olefin such as cis-di-t-butylethylene; a cis-tertiary silyl substituted olefin such as cis-bis(trimethylsilyl)ethylene; and a cis-aryl-substituted olefin such as cis-stilbene or cis-1,2-dinaphthylethylene.
• a bridged olefin such as 2-norbornene, 2,5-norbornad
• acetylene compound there may be specifically mentioned a straight chain acetylene hydrocarbon such as ace: lene, propyne, 1-butyne, 2-putyne, 1-pentyne, 2-pentyne, 1-hexyne, 2-hexyne, 3-hexyne, 1-heptyne, 2-heptyne, 3-heptyne, 1-octyne, 2-octyne, 3-octyne, 4-octyne, 1-nonyne, 2-nonyne, 3-nonyne, 4-nonyne, 1-decyne, 3-decyne or 4-decyne; an alkyl acetylene such as 3,3-dimethylbutyne-l or 2,2,5,5-tetramethylhexyne-3; an aryl acetylene such as phenyl acetylene or di
• a-olefin compound, cis-olefin compound or acetylene compound is added usually in an amount of from 1 to 100 mol, preferably from 3 to 20 mol, per mol of cobalt atoms in the cobalt compound.
• the reason why the partially hydrogenated product of the present invention is obtainable in high selectivity even when the conversion of the conjugated diene is increased, by incorporating the above-mentioned specific a-olefin compound, cis-olefin compound or acetylene compound in the reaction system, is not necessarily clear.
• each of these compounds acts competitively with the partially hydrogenated product, as a compound which has weaker coordinating power to the catalyst than the starting material conjugated diene but stronger coordinating power than the partially hydrogenated product, whereby the coordination of the partially hydrogenated product to the catalyst is preveted in the case where the conversion cf the conjugated diene is high.
• the reaction is usually conducted at a temperature of at most 50°C. If the temperature is higher than 50°C, the production rate of isomers other than the desired product tends to increase.
• the reaction temperature is preferably from -20 to 50°C, more preferably from -5 tc 45°C.
• reaction pressure a pressure from atmospheric pressure to 100 kg/cm2 is usually employed.
• the reaction is conducted usually in the presence of a solvent.
• a solvent any inert solvent may be employed.
• an aromatic hydrocarbon such as toluene, or a halogenated aromatic hydrocarbon such as chlorobenzene, dichlorobenzene, trichlorobenzene or bromobenzene.
• the reaction may be conducted in any manner of a batch system, a semicontinuous system or a continuous system.
• the reaction product may be isolated by a usual separation method such as distillation, extraction or adsorption. When the separation is conducted by distillation, the distillation residue may be recycled for reuse as the catalyst solution.
• bromotris(triphenylphosphine)cobalt (I) complex Into a flask having a capacity of 100 ml, 185 .mg (0.2 mmol) of bromotris(triphenylphosphine)cobalt (I) complex was charged, and after thoroughly flushing the interior of the flask with nitrogen, 20 ml of bromobenzene was added as a solvent. To the bromobenzene solution, 55 ⁇ l, (0.44 mmol) of borontrifluoride etherate was dropwise added under stirring and cooling with ice water.
• the reaction was conducted in the same manner as in Example 1 except that 26 mg (0.2 mmol) of cobalt (II) chloride was used instead of cobalt (II) acetylacetonate, 0.66 ml (0.4-mmol) of a toluene solution containing 13.7% by weight of triisobutylaluminum was used instead of triethylaluminum, and 53 mg (0.4 mmol) of aluminum chloride was employed. About 15 minutes later, absorption of a substantially theoretical amount of hydrogen was observed. The reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 1 except that 71 mg (0.2 mmol) of cobalt (III) acetylacetonate was used instead of cobalt (II) acetylacetonate, 0.53 ml (0.6 mmol) of a toluene solution containing 15% by weight of triethylaluminum and 55 mg (0.41 mmol) of aluminum chloride were employed, and the vigorous stirring was conducted for about 6 hours under cooling with ice water. The reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 1 except that 182 mg (0.6 mmol) of tri-p-tolylphosphine was used instead of triphenylphosphine, and 0.66 ml (0.4 mmol) of a toluene solution containing 13.7% by weight of triisobutylaluminum was used instead of the toluene solution of triethylaluminum. About 3 minutes later, absorption of a substantially theoretical amount of hydrogen was observed. The reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 1 except that 45 mg (0.18 mmol) of cobalt (II) acetylacetonate was used, 253 mg (0.54 mmol) of tris(p-trimethylsilylphenyl)phosphine was used instead of triphenylphosphine, and 0.60 ml (0.36 mmol) of a toluene solution containing 13.7% by weight of was used enstead of the solution of triethylaluminum. About 4 minutes later. absorption of substantially theoretical amount of hydrogen was abserved. The reaction solution was analysed by ges chromotography, Whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 1 for 200 minutes except that the amount of isoprene was changed to 4.0 ml (40 mmol) and the amount of chlorobenzene was changed to 10 ml.
• the reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• the production ratio of 3MBl relative to cobalt atoms in the catalyst was 147 mol/mol-Co.
• the reaction was conducted in the same manner as in Example 1. After the completion of the reaction, the products and feed isoprene were distilled off under reduced pressure by means of a vacuum pump, and under a refreshed hydrogen atmosphere, 0.3 ml (3.0 mmol) of isoprene was added and the reaction was repeated in the same manner as in Example 1. In the fourth repetition, the absorption rate of hydrogen decreased to a level of about a half of the absorption rate in the first operation, and the reaction time required was 10 minutes. The reaction solution after repeating the reaction four times was analyzed by gas chromatography, whereby the following results were obtained.
• Example 1 The hydrogenation reaction of Example 1 was conducted at room temperature (18°C). About 3 minutes later, absorption cf a substantially theoretical amount cf hydrogen was observed. The reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• Example 1 The hydrogenation reaction of Example 1 was conducted in a dry ice-carbontetrachloride bath. About 6 minutes later, absorption of a substantially theoretical amount of hydrogen was observed. The reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• Example 1 The hydrogenation reaction of Example 1 was conducted under atmospheric pressure for 3 hours in an oil bath at 65°C with a dry iee trap provided between the hydrogen inlet and the reactor.
• the reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• reaction was condcted in the same manner as in Example 18 except that 50 mg (0.33 mmol of trifluoro- acid was used instead of trichloroacetic acid. About 18 minutes later, absorption of a substantially theoretical amount of hydrogen was observed. Then, reaction was terminated, and the reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• the hydrogenation reaction was further continued, and the reaction solution was again analyzed when absorption of a substantially theoretical amount of hydrogen was observed, whereby the conversion of IP was found to be 98%, but the production ratio of 3MB1 was as little as 0.4%, and the production ratio of 2MB2 increased to 87.9%.
• the reaction solution was analyzed by gas chromatography, whereby the production ratio of 3MB1 was 82% as in the case of Example 20.
• the reaction was further continued to increase the conversion of IP, and when absorption of a substantially theoretical amount of hydrogen was observed, the reacticn solution was analyzed, whereby the conversion cf IP was 99.4%, and the production ratio of 3MB1 was 82%.
• the production ratios of other reduction products were 4.6% cf 2MB1, 13.8% of 2MB2 and 0.14 of 2MB.
• the reaction was conducted in the same manner as in Example 21 except that the amount of triphenylphosphine was changed to 2.62 g (10 mmol), 0.60 ml (0.46 mmol) of a toluene solution containing 10.0% by weight of triethylaluminum was used as the toluene solution of triethylaluminum, and 0.96 ml (0.34 mmol) of a toluene solution containing 10.0% by weight of ethylaluminum sesquichloride was used as the toluene solution of ethylaluminum sesquichloride.
• the reaction was terminated when absorption of a substantially theoretical amount of hydrogen was observed, and the reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 21 except that 0.60 ml (0.46 mmol) of a toluene solution containing 10.0% by weight of triethylaluminum was used instead of tne toluene solution of triethylaluminum, and 52 mg (0.39 mmol) of aluminum chloride was added instead of the toluene solution of ethylaluminum sesquichloride.
• the reaction was terminated when absorption of a substantially theoretical amount of hydrogen was observed, and the reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 21 except that a flask having a capacity of 1 liter was used, the amount of cobalt (II) acetylacetonate dihydrate was changed to 1.47 g (5.0 mmol), the amount of triphenylphosphine was changed to 32.75 g (125 mmol) the amount of chlcrobenzene was changed t 250 ml, 15.1 ml (11.4 mmol) of a toluene solution containing 10.0% by weight of triethylaluminum was used as the toluene solution of triethylaluminum, 15.5 ml (8.55 mmol) of a toluene solution containing 15.3% by weight of ethylaluminum sesquichloride was used as the toluen solution cf ethylalurinum sesquichloride, and the amount cf isoprene was chanced to 100 ml (1.0 mol).
• the reaction was conducted in the same manner as ir Example 20 except that after an addition of 0.60 ml (0.46 mmol) of a toluene solution containing 10.0% by weight of triethylaluminum as the toluene solution of triethylaluminum, 55 ⁇ l(0.44 mmol) of boron trifluoride etherate was added without using the toluene solution of ethylaluminum sesquichloride, and then isoprene was added.
• the reaction solution was analyzed when the absorption of hydrogen reached about 85% of the theoretical amcunt, whereby the conversion of IP was 85% and the production ratio of 3MB1 was 85%. Further, the reaction was continued to increase the conversion of IP, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the fcllowing results were obtained.
• the reaction was conducted in the same manner as in Example 25 except that the amount of triphenylphosphine was increased to 1.31 g (5.0 mmol).
• the conversion of I? was 85%
• the production ratio of 3MB1 was 85% as in the case of Example 25.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the sems manner as in Example 27 except that the amount of triphenylphosphine was incresed to 1,31 g 16,0 mmol).
• the conversion of IP was 901
• the production ratio of SMSI was 89,40 as in the case of Example 27.
• the conversion of LP was futher increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 20 except that 0.60 ml (0.46 mmol) of a toluene solution containing 10.0% by weight of triethylaluminum was used as the toluene solution of triethylaluminum, 0.96 ml (0.34 mmol) cf a toluene solution containing 10.0% by weight of ethylaluminum sesquichloride was used as the toluene solution of ethylaluminum sesquichloride, and after the addition of isoprene, 0.21 ml (1.6 mmol) of a-methylstyrene was added.
• the reaction was conducted in the same manner as in Example 29 except that 0.18 ml (1.6 mmol) of styrene was used instead of ⁇ -methylstyrene.
• 0.18 ml (1.6 mmol) of styrene was used instead of ⁇ -methylstyrene.
• the reaction solution was analyzed, whereby the conversion of IP was 90%, and the production ratio of 3MBl was 80%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 29 except that 0.25 ml (1.6 mmol) of trimethyl- vinylsilane was used instead of a-methylstyrene.
• 0.25 ml (1.6 mmol) of trimethyl- vinylsilane was used instead of a-methylstyrene.
• the reaction solution was analyzed, whereby the conversion of IP was 90%, and the production ratio of 3MBl was 82%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 29 except that 0.21 ml (1.6 mmol) of 3,3-dimethylbutene-l was used instead of a-methylstyrene.
• 0.21 ml (1.6 mmol) of 3,3-dimethylbutene-l was used instead of a-methylstyrene.
• the reaction solution was analyzed, whereby the conversion of IP was 90%, and the production ratio of 3MBl was 80%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 29 except that 0.22 ml (1.6 mmol) of vinylcyclohexane was used instead of ⁇ -methylstyrene.
• 0.22 ml (1.6 mmol) of vinylcyclohexane was used instead of ⁇ -methylstyrene.
• the reaction solution was analyzed, whereby the conversion of IP was 90%, and the production ratio of 3MBl was 81%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 20 except that 0.60 ml (0.46 mmol) of a toluene solution containing 10.0% by weight of triethylaluminum was used as the toluene solution of triethylaluminum, 0.96 ml (0.34 mmol) of a toluene solution containing 10.0% by weight of ethylaluminum sesquichloride was used as the toluene solution of ethylaluminum sesquichloride, and after the addition of isoprene, 151 mg (1.6 mmol) of 2-norbornene was added.
• the reaction was conducted in the same manner as in Example 34 except that 0.11 ml (0.8 mmol) of dicyclopentadiere was used instead of 2-norbornene.
• the absorption cf hydrogen reached about 90% of the theoretical amount, the reaction solution was analyzed, whereby the conversion of IP was 90%, and the production rammo of 3MBl was 79%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 34 except that 0.08 ml (0.8 mmol) of 2,5-norbornadiene was used instead of 2-norbornene.
• 0.08 ml (0.8 mmol) of 2,5-norbornadiene was used instead of 2-norbornene.
• the reaction solution was analyzed, whereby the conversion of IP was 90%, and the production ratio of 3MBl was 82%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 34 except that 0.28 ml (1.6 mmol) of cis-stilbene was used instead of 2-norbornene.
• 0.28 ml (1.6 mmol) of cis-stilbene was used instead of 2-norbornene.
• the reaction solution was analyzed, whereby the conversion of IP was 90%, and the production ratio of 3MB1 was 82%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 34 except that 288 mg (1.6 mmol) of trans-stilbene was used instead of 2-norbornene.
• the reaction solution was analyze whereby the conversion of IP was 90%, and the production ratio of 3MBL was 81%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were- obtained.
• the reaction was conducted in the same manner as in Example 20 except that 0.60 ml (0.46 mmol) of a toluene solution containing 10.0% by weight of triethylaluminum was used as the toluene solution of triethylaluminum, 0.96 ml (0.34 mmol) of a toluene solution containing 10.0% by weight of ethylaluminum sesquichloride was used as the toluene solution of ethylaluminum sesquichloride, and after the addition of isoprene, 0.18 ml (1.6 mmol) of 3-hexyne was added.
• the reaction was conducted in the same manner as in Example 39 except that 0.23 ml (1.6 mmol) of trimethylsilylacetylene was used instead of 3-hexyne.
• 0.23 ml (1.6 mmol) of trimethylsilylacetylene was used instead of 3-hexyne.
• the reaction solution was analyzed, whereby the conversion of IP was 90%, and the production ratio of 3MB1 was 81%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 39 except that 0.17 ml (1.6 mmol) of phenylacetylene was used instead of 3-hexyne.
• 0.17 ml (1.6 mmol) of phenylacetylene was used instead of 3-hexyne.
• the reaction solution was analyzed, whereby the conversion of IP was 90%, and the production ratio of 3MBl was 83%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 39 except that 235 mg (1.6 mmol) of diphenylacetylene was used instead of 3-hexyne.
• the reaction solution was analyzed, whereby the conversion of IP was 90%, and the production ratio of 3MBl was 81%.
• the conversion of IP was further increased, and when absorption of a substantially theoretical amount of hydrogen was observed, the reaction solution was analyzed, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 43 except that 0.51 ml (3.0 mmol) of myrcene was used instead of 1-vinylcyclohexene, and 20 ml of dichlorobenzene was used as the solvent. Upon expiration of 8 minutes from the initiation of the reaction, the reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 43 except that 38 mg (0.28 mmol) of aluminum chloride was used instead of the toluene solution of ethylaluminum sesquichloride, 0.85 ml (5.0 mmol) cf myrcene was used instead of 1-vinylcyclohexene, and 20 ml of trichlorobenzene was used as the solvent. Upon expiration of 20 minutes from the initiation of the reaction, the reaction solution was analyzed by gas chromatography, whereby the following results were obtained.
• the reaction was conducted in the same manner as in Example 43 except that 0.3 ml (3.0 mmol) of trans-1,3-pentadiene was used instead of 1-vinylcyclohexene. Upon expiration of 11 minutes from the initiation of the reaction, the reaction solution was analyzed by gas chromatography, whereby the following results were obtained.

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